EP0814905B1 - Ruthenium-rhenium/kohle-katalysator für die hydrierung in wässriger lösung - Google Patents

Ruthenium-rhenium/kohle-katalysator für die hydrierung in wässriger lösung Download PDF

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EP0814905B1
EP0814905B1 EP95943406A EP95943406A EP0814905B1 EP 0814905 B1 EP0814905 B1 EP 0814905B1 EP 95943406 A EP95943406 A EP 95943406A EP 95943406 A EP95943406 A EP 95943406A EP 0814905 B1 EP0814905 B1 EP 0814905B1
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ruthenium
rhenium
catalyst
compound
carbon support
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EP0814905A1 (de
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Jo-Ann Theresa Schwartz
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EIDP Inc
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EI Du Pont de Nemours and Co
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/656—Manganese, technetium or rhenium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
    • C07C29/149—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/18—Carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/656—Manganese, technetium or rhenium
    • B01J23/6567—Rhenium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B31/00—Reduction in general
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/17—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds
    • C07C29/177—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds with simultaneous reduction of a carboxy group
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
    • C07D307/06—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms
    • C07D307/08—Preparation of tetrahydrofuran
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/582—Recycling of unreacted starting or intermediate materials

Definitions

  • This invention relates to an improved catalyst and method for using the catalyst for hydrogenation in aqueous solution. More specifically but not by way of limitation, the invention relates to the production of tetrahydrofuran, ⁇ -butyrolactone, 1,4 butanediol and the like from a hydrogenatable precursor such as maleic acid, succinic acid or the like in aqueous solution in the presence of hydrogen and a catalyst consisting essentially of highly dispersed, reduced ruthenium and rhenium on a carbon support.
  • a hydrogenatable precursor such as maleic acid, succinic acid or the like
  • a catalyst consisting essentially of highly dispersed, reduced ruthenium and rhenium on a carbon support.
  • 4,985,572 and 5,149,680 disclose and claim a process for hydrogenating a carboxylic acid or an anhydride thereof to corresponding alcohol and/or carboxylic acid ester using a catalyst composition comprising an alloy of a noble metal of Group VIII and one other metal.
  • a ruthenium and rhenium supported on graphitized carbon is used as a catalyst in a plug flow single pass hydrogenation of acetic acid.
  • Japanese patent application publications (Kokai) 6-157490, 6-179667 and 6-157491 disclose methods of preparing tetrahydrofuran by catalytic hydrogenation of maleic anhydride or maleic acid under milder conditions in the presence of an acidic substance using as catalyst a rhenium compound and a Group VIII metal in the first two references and a ruthenium compound in the latter.
  • Comparative examples in the first two references illustrated the use of a ruthenium and rhenium on carbon catalyst without the acidic substance being present.
  • these proposed catalytic reactions are predominantly conducted in an organic solvent or organic reaction media and not in an aqueous solution phase.
  • the reference distinguishes the claimed subject matter from the previous Pd, Re/Carbon aqueous phase hydrogenation system of the prior art by virtue of specifically claiming the use of a carrier of porous carbon having a BET surface area of at least 2,000 m 2 /g; a concept and limitation that is not characteristic of the Pd, Re/Carbon system of the 4,550,185 and 4,609,636 patents nor is this limitation of any critical significance relative to the present invention.
  • the present invention provides a highly active and robust hydrogenation catalyst system that exhibits high performance during hydrogenation of a hydrogenatable precursor in an aqueous solution. More specifically, the invention provides a ruthenium and rhenium on carbon support catalyst wherein both reduced components exhibit a very high degree of dispersion and consistent compositional ratio when quantitatively analyzed at a spatial resolution on the order of a square nanometer; i.e., any microstructural differences are on the sub-nanometer scale. This apparent atomic or near atomic scale dispersion of the reduced metals results in hydrogenation rates heretofore unattained by other known aqueous phase hydrogenation catalyst systems.
  • the reduced ruthenium and rhenium on carbon support catalyst according to the present invention also exhibits improved longevity sustaining unexpectedly high hydrogenation rates over greater duration with more favourable loss of catalytic activity as a function of time.
  • the present invention provides a method for catalytic hydrogenation of a hydrogenatable precursor in an aqueous solution comprising the steps of:
  • the hydrogenation catalyst according to the present invention involves both ruthenium and rhenium being present on a porous carbon support in a reduced, highly dispersed state.
  • the catalyst comprises at least 0.1% by weight of each metal based on the total weight of the catalyst to insure at least reasonable catalyst activity.
  • the metal loading on the carbon support will be from 0.5% to 10.0% ruthenium and 1.0% to 20.0% rhenium.
  • a preferred catalyst for hydrogenation of maleic acid to THF contains about 1.0% ruthenium and about 4.0% rhenium.
  • the carbon support useful in the present invention can be generally any such material as commonly known and commercially available for use in this art.
  • the carbon catalyst support is a porous particulate solid characterized by a size distribution typically ranging from 5 to 100 microns and a BET surface area typically ranging from a few 100 to nearly 2,000 m 2 /g.
  • the carbon support will be commercially available material having an average particle size of the order of 20 microns and a BET surface area from about 900 to about 1,500 m 2 /g.
  • the catalyst support can be manufactured such as to have a latent acid, neutral or basic pH.
  • the catalyst support can be treated prior to metal deposition by one or more techniques as generally known in the art such as impregnation with alkali metal salts and/or calcination.
  • One such method is to prepare a water solution of a soluble ruthenium compound and a soluble rhenium compound and then add this solution to the carbon support.
  • the water is evaporated thus depositing the ruthenium and the rhenium compounds on the carbon support.
  • the actual method of adding the solution to the support can be by any technique generally known to the art including by way of example but not by way of limitation; immersion, spraying, or the like.
  • the dry or partially dried composite material is then subjected to a reducing atmosphere at elevated temperatures for a time sufficient to reduce both the ruthenium and the rhenium.
  • the dry or partially dried catalyst can then be added to the reaction zone for use as a hydrogenation catalyst.
  • a second related method to the above is to perform the process entirely in the presence of water or the aqueous solution of the hydrogenatable precursor.
  • the water solutions of the ruthenium compound and the rhenium compound are commingled with the solid carbon particle phase while chemical reduction is performed.
  • the resulting catalyst exhibits the ability to sustain hydrogenation of maleic acid in an aqueous solution at STY values in excess of 600 g/kg ⁇ hr at 250°C at 2,000 psig total pressure.
  • This methodology is of particular value and commercial interest in that the co-depositing and co-reduction step can be literally performed in situ in the hydrogenation reactor and can be accomplished in the presence of reactants such as succinic and/or maleic acids.
  • both co-depositing and co-reduction techniques serve to further distinguish the ruthenium, rhenium on carbon catalyst from the prior teaching of palladium, rhenium on carbon in that sequential depositing and reduction of palladium and rhenium is required to produce good hydrogenation catalyst activity.
  • the third method of producing the catalyst is to sequentially deposit and reduce the ruthenium on the carbon support and then add the rhenium compound such as to deposit and reduce the rhenium on the same carbon support. In this manner the pre-reduction of the ruthenium occurs before the depositing and subsequent reduction of rhenium.
  • the intermediate ruthenium on carbon can be achieved either in aqueous solution or in the dry state. Also, this method affords the opportunity to perform the final depositing and reduction of the rhenium compound in situ in the hydrogenation reactor by adding the ruthenium on carbon along with perrhenic acid or the like directly to the hydrogenation reactor.
  • the ruthenium compounds useful in the present invention for preparing the catalyst can be generally any such compound that is either water soluble or can be readily converted to a water soluble or partially water soluble compound that can then be deposited on the carbon support. This would include by way of example but not by way of limitation such compounds as RuCl 3 ⁇ xH 2 O, Ru(NO)(NO 3 ) 3 and the like. Preferably ruthenium trichloride is used.
  • the rhenium compounds useful in the present invention for preparing the catalyst can be generally any such compound that is either water soluble or readily converted to a water soluble or partially water soluble rhenium compound by the action of an oxidizing acid solution, hydrogen peroxide, or the like.
  • the perrhenate aqueous chemistry including the corresponding rhenium oxide deposition is particularly useful.
  • a perrhenic acid solution is employed.
  • the reducing agent employed to chemically reduce the ruthenium and/or rhenium can generally be any such reductant or reducing environment consistent with either liquid phase reduction or vapor phase reduction including by way of example but not by way of limitation; formaldehyde, hydrazine hydrate, hydroxylamine, sodium hypophosphite, sodium formate, glucose, acetaldehyde, sodium borohydride, hydrogen and the like.
  • a vapor phase reduction is employed involving gaseous hydrogen with or without an inert diluent gas such as nitrogen or the like in the presence of the solid catalyst precursor, typically the vapor phase reduction is performed at a temperature range of 100 to 500°C (preferably 250-300°C) at atmospheric pressure.
  • the method of using the highly dispersed, reduced ruthenium and rhenium on carbon catalyst to hydrogenate a hydrogenatable precursor according to the present invention can be performed by various modes of operation as generally known in the art.
  • the overall hydrogenation process can be by use of a fixed bed reactor, various types of agitated slurry reactors, or the like operated in either a batch or continuous mode, wherein an aqueous liquid phase containing the hydrogenatable precursor is in contact with a gaseous phase containing hydrogen at elevated pressure and the particulate solid catalyst.
  • Such hydrogenation reactions are performed at temperatures from about 100°C to about 300°C in sealed reactors maintained at pressures from about 1,000 to about 3,000 psig.
  • a hydrogenatable precursor can be, in the broadest sense, any compound or material that can be chemically reduced by hydrogenation or hydrogen up-take. This would include, in particular but again not by limitation, various organic compounds containing unsaturation or oxygenated organic functional groups or both.
  • aqueous phase catalytic hydrogenation of maleic acid to ⁇ -butyrolactone and tetrahydrofuran is illustrative of the utility of the method according to the present invention.
  • various products of the sequential hydrogenation reaction are also potential hydrogenatable precursors.
  • the overall selectivity to THF production can be significantly influenced by optimizing reaction conditions including maintaining adequate acidity thus favoring ring closure and cyclic ether production at the expense of diol production, continuous vapor removal of the more volatile products, and subsequent separation and recycle of the lactone.
  • the ⁇ -butyrolactone can be viewed as either a co-product or as a recycled hydrogenatable precursor reactant.
  • the catalyst of the instant invention involves the respective metals present on the catalyst support as an apparent atomic or near atomic scale dispersion.
  • observations and measurements do not exclude the presence of additional microstructure at dimensions larger than the nanometer limit, nor observable changes in the microstructure at slightly above the nanometer level associated with the choice of methods of preparation and with aging of the catalyst during use as well as undetectable labile structural features below the nanometer observation limit (all of which are presently felt to be to some degree characteristic of the instant catalyst system).
  • imageable ruthenium during use is generally of the order of the average pore size of the porous carbon support (i.e., typically 20 ⁇ or the like) which is still a more highly dispersed state than that previously associated with prior art catalyst systems such as palladium and rhenium on carbon.
  • an imageable ruthenium may be observed depending on the method of preparation of the catalyst.
  • a catalyst made by sequential deposition and reduction involving ruthenium being deposited and reduced prior to deposition and reduction of rhenium may exhibit some imageable ruthenium microstructure at a few nanometers or slightly larger size.
  • the deposition and reduction of ruthenium in the absence of rhenium may produce detectable ruthenium ensembles not associated with the microporous structure of the carbon and not necessarily detrimental to the development of the desirable high activity catalyst felt to be associated with the highly dispersed state of the metals at constant composition ratio.
  • the co-deposited and subsequently co-reduced catalyst is remarkably free of any imageable phase or surface crystallite microstructure and as such is felt to be the preferred catalyst for purposes of the instant invention.
  • the mixture was dried over night at 110°C at reduced pressure (in vacuo) with a nitrogen purge.
  • the dried catalyst was then placed in 150 cc quartz boats in a 1500 cc, 6.35 cm (2.5 inch) diameter, quartz tube oriented horizontally in a tube furnace.
  • a nitrogen purge was carried out at room temperature for 15 minutes at a flow of 500 cc/min.
  • the flow was switched 100 cc/min of helium and held for 25 minutes.
  • the temperature was then ramped to 150 °C for one hour.
  • 100 cc/min of hydrogen was added to the flow and this was held for one hour at 150 °C.
  • the temperature was then raised to 300 °C with 1:1 H 2 -He flow and then held for eight hours. After this time period the flow was switched back to helium and the catalyst was cooled in helium overnight. Once the temperature was less than 50 °C, the catalyst was passivated for 30 minutes in flowing 1% O 2 in N 2 .
  • the resulting 1 wt.% Ru and 4 wt.% Re on carbon catalyst was tested in the reactor as described in following examples.
  • the catalyst when examined by conventional x-ray diffraction and high resolution transmission electron microscopy showed no imageable metal crystallite structure (i.e., no separate structures >10 ⁇ in size other than background carbon structure); yet, chemical analysis with EDX confirms the one to four weight ratio of ruthenium to rhenium is essentially uniformly present across the carbon particle and from particle to particle.
  • the hydrogen used was CP grade from a cylinder, the nitrogen was from a cylinder, the succinic acid was Baker Analyzed reagent grade crystal and the water was deionized water.
  • Seven weight percent solutions of succinic acid were made in 500 gram batches by dissolving 35 grams of succinic acid in 465 grams of deionized water. The solutions were heated to 30°C to completely dissolve the succinic acid. The solutions were then titrated to precisely determine the percent acid.
  • the procedure employed involved adding the catalyst (typically about 0.1 to 0.5 grams) into the reactor followed by 35 grams of 7% succinic acid solution. The head was then placed on the reactor and bolted into place and torque down.
  • the volatile products and water were swept out of the reactor at a rate controlled by the hydrogen feed rate.
  • the hydrogen feed rate was adjusted so that the amount of water carried out with the exiting hydrogen gas was balanced with the amount of water added with the maleic acid feed and the amount produced by the reaction.
  • the reactor level was maintained constant at 100-200 cc. In all cases an excess of hydrogen was fed relative to the amount consumed by the reaction and the hydrogen feed rate was shown not to influence catalyst performance.
  • the maleic acid solution was fed at a low initial feed rate and was increased by 2-3 cc/hr about every 8 hours until the acid level in the reactor reached 8%. After this the maleic acid feed rate was adjusted as necessary to maintain the reactor acid level between 6-10%.
  • the runs were made without interruption for up to several weeks. and time intervals during steady state operation were selected for analysis. generally of 8 to 24 hours duration.
  • the product composition data generated during steady state operation was averaged to give the average production rates (g/hr) of THF (tetrahydrofuran), BDO (1,4-butanediol), GBL (gamma-butyrolactone), PrOH (n-propyl alcohol), BuOH (n-butyl alcohol), and alkanes (primarily butane and methane).
  • the product composition was measured by condensing a portion of the volatilized products and water in the exit gas stream and collecting the liquid product.
  • the volume of liquid product collected each hour was measured, and its composition analyzed using a calibrated gas chromtograph (GC) equipped with a flame ionization detector.
  • GC gas chromtograph
  • the remaining uncondensed products (THF and alkanes) still in the exit gas stream were analyzed by measuring the gas flow rate and then analyzing the composition of the gas stream every two hours using GC procedures similar to those used for liquid analysis.
  • the reactor contents were sampled every four hours and analyzed by GC and titration. Titration with sodium hydroxide was used to monitor the acid concentration in the reactor and the results are reported as percent by weight of succinic acid.
  • the GC analysis was carried out using a Supelcowax 10 capillary column (30 m x 0.052 mm) which was maintained at 75°C for 5 minutes after injection and then heated at 10°C per minute to a final temperature of 200°C.
  • the combination of these three analyses permits calculation of the catalyst performance in terms of space-time-yield (STY) (calculated as grams of THF produced per kilogram of catalyst per hour), product selectivity and the mass balance for each run.
  • STY space-time-yield
  • the catalyst used was 3.5 grams (dry weight) of a 1% ruthenium and 4% rhenium on a carbon support.
  • the initial maleic acid feed rate was 6 cc/hr, and this was increased in 2 cc/hr increments up to 20 cc/hr, at which point the acid level in the reactor reached 8%. After this the feed rate was adjusted to maintain the acid level at 6-10%.
  • the initial THF production rate (at the lowest maleic acid feed rate) was 200 STY (g THF/kg catalyst hr). As the acid feed rate was increased the production rate continued to increase reaching as high as 1,200 STY by the time the feed rate reached 20 cc/hr. Over the next three weeks of operation the activity slowly declined, finally reaching a THF production rate of about 600 STY.
  • a second comparative run was made as in the above run, except the catalyst was replaced with 10 g of a 1% palladium and 4% rhenium of the same carbon support.
  • the maleic acid feed was started at 12 cc/hr and was increased over five days to 28 cc/hr. Over this period the acid level in the reactor increased up to 5%, and the THF production rate increased up to a maximum of 495 STY.
  • the phrase refers to characterizing the highly active and robust hydrogenation catalyst system according to the instant invention in terms of the catalysts ability to sustain the production of THF in a continuous mode of operation wherein the volatile product is swept from the reactor by the excess gaseous phase containing the reactant hydrogen all at the specified conditions (i.e., 250°C and 13.79 MPag (2,000 psig) total pressure).
  • the characterization reaction is conducted such as to afford the catalyst the opportunity to exhibit full reaction potential and not be subject to stoichiometric limitations of either reactant (i.e., the hydrogen or the hydrogenatable precursor).
  • the rate of flow of reactants to the reactor are adjusted (increased) until the catalyst is being utilized to its fullest extent. Typically this is achieved by monitoring the residual acid content of the reactor and increasing the reactant flow until at least about a 5% acid or higher steady state is present in the reactor. At acid concentrations below this value the STY will not be optimized and the tendency to over hydrogenate the product will also reduce the selectivity to THF. Experience indicates that operating at or above this residual acid level produces STY values heretofore unachieved by prior art catalyst systems. Residual reactor acid levels as high as twenty percent have been successfully achieved but as a pragmatic consideration succinic acid solutions of this concentration will solidify unless maintained at high temperature.
  • the catalyst system of the instant invention affords and provides a method for sustaining catalytic hydrogenation of maleic acid dissolved in water at space-time-yields heretofore unachievable. Furthermore, this aqueous phase hydrogenation is achieved without the use of external additives or agents such as the presence of strong acid nor does the hydrogenation depend on the use of extremely high BET surface area carbon support.
  • the instant catalyst and method of use is amenable to a continuous mode of commercial operation involving the addition of maleic acid to the catalytic reactor as an aqueous solution and the continuous recovery of gaseous product by sweeping the other reactant, hydrogen, through the reaction zone, all of which represent and translate into a significant economic advantage, particularly at the commercial scale associated with contemporary THF production.
  • Further cost savings are realised by virtue of the inherent lower cost of the respective metals of the catalyst and the lower capital investment per unit production associated with the high STY of the catalyst.
  • the discovery of the high dispersion at the nanometer or sub-nanometer scale affords a method of characterising the catalyst and its respective performance which in turn has pragmatic value for operating a commercial scale plant.

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Claims (7)

  1. Ein Verfahren zur katalytischen Hydrierung einer hydrierbaren Vorstufe in einer wäßrigen Lösung, das die Schritte beinhaltet:
    (a) Hydrierung einer hydrierbaren Vorstufe in einer wäßrigen Lösung in Gegenwart von Wasserstoff und einem Katalysator, wobei der Katalysator im wesentlichen aus wenigstens 0,1 Gew.-% Ruthenium und wenigstens 0,1 Gew.-% Rhenium besteht, die auf Kohlenstoff aufgebracht sind bzw. von Kohlenstoff getragen werden, wobei die Prozentangaben sich auf das Gesamtgewicht des Katalysators mit Trägerstoff (supported catalyst) beziehen, worin sowohl Ruthenium als auch Rhenium in einem stark dispergierten reduzierten Zustand vorhanden sind, charakterisiert durch Röntgenstrahlbeugung und hochauflösende Transmissions-Elektronenmikroskopie, die keine abbildbare Metallkristallitstruktur zeigt bzw. zeigen, wobei der Kohlenstoffträger durch eine BET-Oberfläche von weniger als 2000 m2/g charakterisiert ist; und dann
    (b) Rückgewinnen bzw. Gewinnen von wenigstens einem hydrierten Produkt.
  2. Ein Verfahren nach Anspruch 1, worin die hydrierbare Vorstufe ausgewählt ist aus der Gruppe bestehend aus Maleinsäure, Maleinsäureanhydrid, Fumarsäure, Succinsäure, Maleinsäure, den diesen Säuren entsprechenden Estern, γ-Butyrolacton und Mischungen davon.
  3. Ein Verfahren nach Anspruch 1, worin sowohl das Ruthenium als auch das Rhenium im Sub-Nanometerbereich bzw. -maßstab dispergiert sind.
  4. Ein Verfahren nach Anspruch 1, worin sowohl das Ruthenium als auch das Rhenium hochdispergiert sind mit einem konstanten Zusammensetzungsverhältnis von Ruthenium zu Rhenium, wenn es durch STEM über den Katalysatorpartikel mit einer räumlichen Auflösung in der Größenordnung von einem Quadratnanometer analysiert wird.
  5. Ein Verfahren nach Anspruch 1, worin der Katalysator durch das Verfahren hergestellt wird, das in dieser Abfolge die Schritte beinhaltet: Abscheiden bzw. Ablagern sowohl einer Rutheniumverbindung als auch einer Rheniumverbindung auf einem Kohlenstoffträger; Trocknen des Kohlenstoffträgers, der sowohl die Rutheniumverbindung als auch die Rheniumverbindung enthält; und anschließend Reduzieren des Rutheniums und des Rheniums.
  6. Ein Verfahren nach Anspruch 1, worin der Katalysator durch das Verfahren hergestellt wird, das in dieser Abfolge die Schritte beinhaltet: Abscheiden bzw. Ablagern sowohl einer Rutheniumverbindung als auch einer Rheniumverbindung auf einem Kohlenstoffträger und anschließend Reduzieren des Rutheniums und des Rheniums in situ in einem Hydrierreaktor, worin das Hydrieren der hydrierbaren Vorstufe in einer wäßrigen Lösung stattfindet.
  7. Ein Verfahren nach Anspruch 1, worin der Katalysator durch das Verfahren hergestellt wird, das in dieser Abfolge die Schritte beinhaltet: Abscheiden bzw. Ablagern einer Rutheniumverbindung auf einem Kohlenstoffträger; Trocknen des Kohlenstoffträgers, der die Rutheniumverbindung enthält und anschließend Reduzieren des Rutheniums, bevor eine Rheniumverbindung auf dem Kohlenstoffträger abgeschieden bzw. abgelagert und reduziert wird.
EP95943406A 1995-03-03 1995-12-13 Ruthenium-rhenium/kohle-katalysator für die hydrierung in wässriger lösung Expired - Lifetime EP0814905B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US08/398,638 US5478952A (en) 1995-03-03 1995-03-03 Ru,Re/carbon catalyst for hydrogenation in aqueous solution
US398638 1995-03-03
PCT/US1995/016110 WO1996027436A1 (en) 1995-03-03 1995-12-13 IMPROVED Ru, Re/CARBON CATALYST FOR HYDROGENATION IN AQUEOUS SOLUTION

Publications (2)

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EP0814905A1 EP0814905A1 (de) 1998-01-07
EP0814905B1 true EP0814905B1 (de) 2000-04-05

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Country Link
US (1) US5478952A (de)
EP (1) EP0814905B1 (de)
JP (1) JPH11500958A (de)
KR (2) KR100367388B1 (de)
CN (1) CN1100610C (de)
AU (1) AU4468196A (de)
DE (1) DE69516181T2 (de)
ES (1) ES2145325T3 (de)
TW (1) TW324669B (de)
WO (1) WO1996027436A1 (de)

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CN1100610C (zh) 2003-02-05
DE69516181T2 (de) 2000-12-21
TW324669B (de) 1998-01-11
EP0814905A1 (de) 1998-01-07
KR19980702698A (ko) 1998-08-05
WO1996027436A1 (en) 1996-09-12
DE69516181D1 (de) 2000-05-11
JPH11500958A (ja) 1999-01-26
ES2145325T3 (es) 2000-07-01
KR19987002698A (de) 1998-08-05
KR100367388B1 (ko) 2003-02-19
CN1177310A (zh) 1998-03-25
AU4468196A (en) 1996-09-23
US5478952A (en) 1995-12-26

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